Azobiphenylcarbonylaminoanthraquinone compounds



United States Patent AZOBIPHENYLCARBONYLAMINOANTHRA- QUINONE COMPOUNDS Joseph Deinet, Glassboro, N. J., assignor to E. I du Pont de Nemours and Company, Wilmington, Del., a corporation of Delaware No Drawing. Application July 9, 1951, Serial No. 235,891

6 Claims. (Cl. 260157) zole group and which carry at least one sulfonic acid group in the anthraquinone radicals. The compounds of this invention have the general formula:

in which X stands for a member of the group consisting of O and S; y stands for a member of the group consisting of hydrogen, halogen, and the sulfonic acid group; and R stands for an anthraquinonyl radical which is unsubstituted or which carries a substituent of the group consisting of halogen, methyl, methoxy and benzoylamino groups-there being present in the molecule, as formulated, at least one sulfonic acid group attached to the beta position of one of the anthraquinone nucleibut in no case does either anthraquinone nucleus carry more than one sulfonic acid group. By the term sulfonic acid group, I refer to the sulfonic acid group as such and to the alkali metal salts of such acid. More particularly, 1 refer to the more common sodium and potassium salts.

In United States Patents 2,559,669 and 2,587,908, a related group of vat dyes of the anthraquinone oxazole series is disclosed. These compounds dye cotton and related fibers from alkaline hydrosulfite vats in yellow shades which exhibit desirable brightness as well as good fastness properties. It has been found, however, that these dyes are deficient in printing properties, possibly because of poor solubility in the printing gum, for when printed they do not yield the strong and bright yellow shades characteristic of the vat dyeings of these colors.

It is, therefore, an object of the present invention to produce new and valuable dyes of the anthraquinone vat dye class which will print, aswell as dye, cellulose and related fibers in desirable yellow shades and exhibit good brightness, tinctorial strength and fastness properties. It is a more specific object of the invention to produce anthraquinone dyes which are 4,4'-substituted azobiphenyl compounds carrying in the molecule both an aminoanthraquinone group and an anthraquinone'oxazole or an anthraquinone thiazole group, one or both of said ice valuable vat dyes of the anthraquinone series which may be produced from readily obtainable amino-anthraquinone,

sulfonic acids or amino-halogen-anthraquinone sulfonic acids.

The oxazole compounds are best prepared in a nonreactive medium by condensing 4,4-aZobiphenyl-4,4- dicarboxylic acid chloride with a 2-amino-1-halogen anthraquinone or a Z-amino-I-halogen anthraquinone-sulfonic acid and further condensing the intermediate monoacid chloride so obtained in situ with an amino-anthraquinone sulfonic acid or with an amino-anthraquinone, and then ring-closing to the oxazole compound inthe presence of an acid binding agent and a catalyst at elevatedtemperature, preferably in the range of from 180 C. to 220 C.

Either the amino-anthraquinone containing halogen in its l-position or the amino-anthraquinone not substituted I in l-position may be condensed first with the azobiphenylanthraquinone radicals carrying a sulfonic acid radical.

It is a still further object of the invention to produce new under agitation and maintained for 12 to 20 hours.

dicarbonyl chloride followed by condensation of the resulting mono carbonyl chloride with the amine of alter- ,nate choice and then ring-closure of the bis-amide to the 'oxazole amide end product.

In an alternate route the oxazole ring of the mono carbonyl chloride is formed prior to condensation with the second mol of an aminoanthraquinone.

The thiazole compounds are best prepared by condensing 4,4'-azobiphenyl 4",4"-dicarboxylic acid chloride with an amino-anthraquinone sulfonic acid (mole per mole) and further condensing the intermediate mono acid chloride with a 2-amino-1-mercapto-(Na)-anthraquinone at elevated temperature preferably in the range of from 180 C. to 220 C. The products may be conditioned for dyeing or printing in the usual manner, such as by milling or acid pasting with or without purification by bleaching with sodium hypochlorite. These new dyes are generally yellow pastes which dye and print cotton or related fibers in strong bright shades and exhibit good light-fastness and tinctorial strength. Their wet-fastness is of the same high order as found in most anthraquinone vat colors.

The following examples are given to illustrate the invention. The parts used are by weight.

Example 1 1200 parts of nitrobenzene, 2 parts of pyridine, 50 parts of 4,4-azobiphenyl-4",4'"-dicarboxylic acid and 43 parts of thionyl chloride are heated to 98 C. to 100 C. The mass is then air blown for one half hour to remove the excess of thionyl chloride. After cooling to 40 0., there are added 30.5 parts of 1-chloro-2-amino-anthraquinone. The mass is then heated to C. and maintained for six hours. After cooling to 25 C., there are added 38.5 parts of 2-amino-anthraquinone-3-sulfonicacid (sodium salt). The reaction is then heated to 208 C. and maintained at this temperature for one hour. It is then cooled to 50 C. and 50 parts of sodium carbonate, 50 parts of potassium acetate, one part of cupric acetate and one part of cuprous chloride are added. The mass is heated to 208 C. to 210 C., and maintained for two and one-half hours. It is then cooled to 50 C., filtered, the filter cake washed with nitrobenzene, alcohol and hot water in turn and dried. The product is then acid pasted by drowning a concentrated sulfuric acid solution of the color in water, thereafter filtered, washed acid-free and purified by bleaching with sodium hypochlorite. It forms a bright yellow paste and dyes and prints cotton or related fibers in strong bright yellow shades of excellent fastness properties 3 4 Thev dye has the formula; C. and. maintained at this temperature for one and one-half.

?-C =N- CO-HN- NaOaS Example II hours. The mass is then cooled to 100 C. and 50 parts Fifty parts, of 4,4, aZObipheny1. 4.4,u dicarboxylic acid of sodium carbonate, 50 parts of potassium acetate, one are converted to the acid chloride asin Example I. 30.5 Part of cupnc acetate.and one Part of 39 Chloride parts of l-chloro-2-amino-anthraquinone' are added and i The mass 18 then heated to 210 i the mass heated to 13.80 C. to 140 C. and maintained talne for two and one-half hours. After coolmg to 0 C., the mass is filtered and the filter cake washed with nitrobenzene, alcohol and hot water in turn and dried. The product is then acid pasted and purified by bleaching 20 with sodium hypochlorite. It forms a bright yellow paste at this temperature for six hours. The mass is then cooled to 50 C. and 40.5 parts of l-amino-anthraquinone-d-sulfonic acid (K salt) are added. The reaction mass is-then heated to 208 C. and maintained at this temperature and dyes and prints cotton-01 related. fibers in strong for, one and one-half hours. The mass is then cooled to bright yellow shades ofexcellent fastness properties. 100 C. and 50 parts of sodium carbonate, 50 parts of The dyein the form ot'the sodiumsalt has the formula:

0 0-0 N=N Y COHN' o il l] i N -SO;Na

potassium acetate, 1 part of cupric acetate and 1 part of Example IV cuprous chloride are added. The mass. isthen. heated to 210 C. and maintained at this temperature for three, fifty-five Parts of 4A'azoblpheny14 dlcarboxyhc hours It isrthen 60016 d to C the mass filtered acid (sodium salt) are converted to the acidchloride the filter cake washed with nitrobenzene, alcohol and hot as m Exlflmplfle Parts of z'ammo'amhraqumone' water in turn and. dried. The product is then acidpasted 3sulfomc acld (Na Sam are added and the mass heated and purified by bleaching with sodium hypochlorite. It 40 F 1700 and mainotained for hours- The mass forms a bright yellow paste and dyes and prints cottonin 15 then Cooled to and 43 Parts of strong bright yellow shadesofi excellent fastness properties. amino-anthraqllinofie'3-sulfonic acid (Sodium are The dye in the form of the sodium salt has the formula; added. The reaction mass is then heated to 208 C.

o o fi -N.=N 0 o,onr 1 o V-SOQNB Example, III and maintained at this, temperature for one and onehalf hours. The mass is then cooled to 100 C. and 1250parts. of. mtrobenzene, 2 partsof pyridine, parts i of 414 azobiphenyb 4n4ru dicarbcxylic.aci d so dium; s alt) 50 parts of sodium carbonate, 5.0 parts of potassium y I acetate, 1' part of cupric; acetate. and 1' part of cuprous g g gi' g g;s g gj i gl z g gfisggig g gi g chloride are added. The mass is then. heated to 210 g i C. and maintained for threehours. After cooling to temperature for 12 to. 20. hours. The mass 15 then air 50 C the mass is filtered. the filter cake Washed. blown for one-half hour to remove excess of thionyl 6Q chlorida After cooling: to C there added 264 with nitrobenzene, alcohol, and water in turn, and dried. parts of l-amino-anthraquinone. and the mass heated. to is then add ,P and Purified bleach 138." c. to 140 c. and maintained at this temperature s with sodium hypochlorite- It fbrms. bright yellow for six hours, After cooling. to; 501 6., there are added P and y and PYiIlts cotton in Strong bright Shades 50. parts of l-bromo-Z-amino-anthraquinonet-sulfonic 65 of excellent fastness properties.

acid (.K salt). The reaction mass is. then heated to 208 The dye has theformula:

2,719,898'. a e r I Example V The mass is then heated to 208 C. andmaintained at v n m this temperature for one and one-half hours. The mass Fifty-five parts of 4,4'-azob1phenyl-4 ,4 -d1carboxyl1c o acid (sodium salt) are converted to the acid chloride ls then cooled to 100 and 50 parts of sodugm as in Example III 26.5 parts of Z-amino-anthraquinone bonate 50 parts of potasslum acetate. one part cupnc I added and mass heated to C and main acetate and one part of cuprous chloride are added. The fai hed at this temperature for six hours The mass is mass is then heated to 0 and maiptained at this then cooled to 50 C. and 48 parts of l-bromo-Z-aminotemperature for three hours After coolmg to 50 the mass is filtered and the filter cake is washed with i gf zg figg g l g fig iza g zfi z: igg ggg nitrobenzene, alcohol and water in turn and dried. The

- 1 product is then acid pasted and purified. by bleaching 58 832 g g g g gg gg' g i lgiig igf gfigg with so diumhypochlorite. It forms a bright yellow paste of potassium acetate, one part of cupric acetate and one and 1s ldemlcal wlth that of Example part of cuprous chloride are added. The mass is then Example VH1 heated to 210 C. and maintained for three hours. After cooling to 50 C., the mass is filtered and the filter cake 1200 Parts Of llltl'obefllelle, 2 Parts Of pyr 55 washed with nitrobenzene, alcohol and water in turn Parts Of P Y Y add 61110- and d i d Th product i th n id pasted d purified ride and 30.8 parts of 1-amino-6-chloro-anthraquinone by bleaching with sodium hypochlorite. It forms a bright are heated together while agitating to 160 C. to 165 C.

yellow paste and dyes and prints cotton in strong bright and maintained for one and one-half hours. The mass shades of excellent fastness properties, is then cooled to 50 C. and 49 parts of 1-bromo-2- The dye has the formula: amino-anthraquinone-3-su1fonic acid (sodium salt) are 0 o--0 N=N o 0-HN I I SOiNa Example VI added. The reaction mass is then heated to 208 C. and

maintained for one hour. It is then cooled to 100 C. Fifty-five parts of 4,4'-azobiphenyl-4",4-dicarboxylic and 50 parts of sodium carbonate, 50 parts of potasacid (sodium salt) are converted .to the acid chloride g sium acetate, one part of cupric acetate and one part as in Example III. 38.5 parts of 2-amino -anthraquinoneof cuprous chloride are added. The mass is then heated 3-sulfonic acid (Na salt) are added and the mass heated t 208 C, to 210 C. and maintai ed for two hour to 170 C. and maintained for three hours. The mass It is then cooled to 50 C., filtered, and the cake washed is then cooled to 50 C. and 33 parts of l-mercaptowith nitrobenzene, alcohol, and hot water in turn and q are added- The 3 then dried. The product is then acid pasted and purimass is then slowly heated to 208 C. and maintained fl d by bleaching with diu hypochlorite, It forms o O e 110111 After Cooling t0 t mass a yellow paste and dyes and prints cotton andrelated filtered and the filter cake Was ed h llltrobenlene, fibers in strong bright yellow shades of excellent fastalcohol and hot water in turn and dried. The product Hess ti is then acid pasted and purified by bleaching with sodium 45 Th dye ha the formula;

SOINB Cl hypochlorite. It forms a yellow paste and dyes and Exam le IX prints cotton or related fibers in strong bright yellow p shades of excellent fastness properties. 1200 Parts of Pitrobenzene, 2 Parts of Pyridine, 55

The dye has the formula: 5 parts of 4,4-azob1phenyl-4",4"-d1carboxylic acid chloo N=N oo-HN m INMOS Example VII ride and 32.5 parts of -1-amino-anthraquinone-6-car- J m boxylic acid are heated together to 170 C. and main- Fift -five arts of 4,4'-azob1phenyl-4 ,4 -d1carboxylic a acid Salt) are converted to the acid chloride tamed for four hours. The mass 1s then cooled to 50 C. as in Example III. 38.5 parts of Z-amino-anthraquinone- 49 Parts P n? 3-sulfonic acid (Na salt) are added and the mass heated fomc acld (sodlum l are addeds 18 then to 170 C. and maintained at this temperature for three heated to a maintaillfid for one and -h l hours. The mass is then cooled to 25 C. and 30.5 hours. It is then cooled to 100 C. and 50 parts of soparts of 1-chloro-2-amino-anthraquinone are added. dium carbonate, 50 parts of potassium acetate, one part of cupric acetate and one part of cuprous chloride are 205 C. and maintained for one and one-half hours. added. The mass is then heated to 210 C. and main- The masais then. cooled to 120 C. and. 50 parts ofisotained at this temperature for two and one-half. hours. dium carbonate, 50 parts of potassium acetate, 1 part It is then cooled to 50 C., filtered, and the filter cake of cupric acetate and 1 part of. cupro us chloride are washed with nitrobenzene, alcohol, and hot water in turn 5 added. The mass is then heated to 2L0 C. and mainand dried. The product is then acid pasted and purified tainedat this temperature for three and one-half hours. by bleaching with sodium hypochlorite. It forms a bright The reaction: mass is then: cooled to 50 C., filtered, the yellow paste and dyes and prints cotton in strong bright filter cake washed with nitrohenzene', alcohol and water yellow shades of excellent fastness properties. in turn and dried The product, upon acid pasting and The dye has the-formula: 1O bleaching with sodium hypochlorite, forms a bright ye1-= O OC N=N GOHN O 403m I c0011.

pl low paste and dyes and printscotton in bright yellow 1200 parts of nitrobenzene, 2 parts of pyridine, 50 Shades of excellent fasmess P p parts of 4,4-azobiphenyl-4",4'"-dicarboxylic acid chlo- The Y has the formula:

O O 0*?!) N\=N' -HN ride and 37.5 parts of 1'-amino-5benzoylaminoanthra- Ex l XII quinone are heated together while agitating to 170" C. The mass is then cooled to 60 C. and 44 parts of 1b'rorno2 amino-anthraquihone-3sulfonic acid (sodium salt)- are added. The mass is then' heated to 205 C. and maintained for one hour. It is then cooled to' 100 C. 40 and 50 parts of sodiumcarbonate, 50 parts of potassium" acetate, one part of cupric acetate and one part of cuprouschloride are added. The mass is then heatedto 210 C. and maintained for two and one-half hours; It is then cooled to 50 C., filtered, and' the filter cake Washed with nitrobenzene, alcohol and hot Water in turn and dried. The product is then acid pasted: and purified by 1,000 parts of nitrobenzene, 2 parts of pyridine, 42.2 parts of 4,4'-azcbiphenylz-4 ,4'-dicarboxylic acid and 40 parts of thionyl chloride are heated together to 98 C. and maintain'ed atthis temperature for fifteen hours. The mass in then air blown for one: hour to remove excess of thionyl chloride. After cooling to 0., there are added 3-2L5partsof 2-amino-anthraquinone-3sulfonic acid (sodium. salt) fine powder and: the. mass is heated to 200 C. and; maintained at this temperature for one hour. The mass is then cooled to 50 C. and 48.3 parts of 1,3- dibromo 2 amino anthraquinone 6 sulfonic acid bleaching. with sodium hypochlorite. It forms an bright (sodium salon fine powdr f added. and thfi mass is yellow Paste and dyes and prints cotton in Strong bright heated to 210 C. and maintained at this temperature for ll h d f excellent f t properties 50 one-and one half-hours. The mass is then cooled to 50 The dye has'the formula: C.. and 45. parts of sodium carbonate, 45 parts of potas- O Ofi ,-N=N C OHN Example Xl sium acetate, 1 part of cupric' acetateand 1 part of cuprous I b 1 t: of ridine, 3O chloride are'added. '1ihe'mass'1s then heated to 210 i gg fi I 6 g i fi g g giigia ggg andmsll6r Parts of, and maintained at this temperature for three hours. The 44'-azobipheny141",4-dicarboxylic acid: chloride are reaction mass isthen'wole'd 105090 filtered; the'filter h eated together at C to C. and mai tai d cake washed with nitroben'zene; alcoholand'water in turn for six hours. The mass is then cooled to. 30 C. and and dfiedi pl fi p 'p afldbleachillg" 385 parts of 2-ami'ndanthraquinone-6 sulfonic acid' (Na. p p p salt) fine powder are added and" the mass is heated to 75 d'ye'sand prints cotton in bright yellow shades.

- with" sodium hypochloriteform's bright yellow paste and The dye has the formula:

When 2-amino-anthraquinone-3-sulfonic acid (Na salt) in the above example is replaced by Z-amino-anthraquinone- 6-sulf0nic acid (Na salt), one obtains the product having the following formula:

This product, upon acid pasting and bleaching with sodium hypochlorite, forms a bright yellow paste and dyes and prints cotton or related fibers in bright yellow shades of excellent fastness properties.

As illustrated in the above examples, the dyes of this invention may carry one or two sulfonic acid groups but when two sulfonic acid groups are present, they should not be in the same anthraquinone nucleus. In preparing these compounds, particularly where the amino-anthra quinone carries the sulfonic acid group in either the 6 or 7 position, the normal occurring mixture of 1-amino-6 and 7-sulfo anthraquinone or the 2-amino-6 and 7-sulfoanthraquinone may be employed or they may be separated and the individual isomers may be employed as desired.

The specific examples given above are merely illustrative of the general invention which is formulated in the introduction of the specification. Other substituted 1- mercapto-Z-amino-anthraquinones may be employed in place of the one specifically disclosed inExample, ,VI ,including sulfonic acid derivatives of such compounds. 1:

Mercapto 2 amino anthraquinone 3 7 sulfonic acid is an available intermediate illustrating this latter class In the anthraquinone thiazole substituted azobiphenyl compounds of this invention, the carbonyl-aminoanthraquinone group may be any of those groups disclosed in the specific examples illustrating the oxazole types or any of the further substituted compounds hereinafter mentioned.

In preparing the compounds containing the oxazole ring, any of the 1,3-dihalogen-Z-amino-anthraquinone compounds which are available may be employed such as the 1,3 dichloro 2 amino anthraquinone; 1,3- dibromo 2 amino anthraquinone; 1 bromo 2 amino 3 chloroanthraquinone; and 1 chloro 2- amino 3 bromoanthraquinone. If it is desired that further halogen be present in the anthraquinone radical, which forms the oxazole portion of the molecule, higher halogen substituted Z-aminO-anthraquinone compounds may be employed.

The anthraquinone group connected with the carbonylamino radical may carry other monovalent substituents zoylamino radicals. The aminoanthraquinones carrying these radicals are readily available anthraquinone vat dye intermediates. Further illustrative of the aminoanthraquinones that may be used in the above examples in place O 0 v LEN ()INB of those specifically mentioned are l-amino-4-methoxy-; anthraquinone; 1-amino-4- or 8-benzoylamino-anthraquinone; and l-amino-2-methyl-anthraquinone. .Although' chlorine and bromine are the typical examples of the halogen substituents remaining in the anthraquinone nucleus of the dyestufi, it will be obvious that, if desired, other halogen substituted aminoanthraquinones may be employed to produce dyes which contain in the final dye- ,stuif other halogens.

Because of the presence of thesulfonic acid group in the compounds of this invention, they can be purified'by vatting without acid pasting, and if desired they may be' bleached with sodium hypochlorite directly in the alka-j line vat solution, although, as illustrated in the'exarnples, the usual acid pasting and hypochlorite bleach may be used.

I claim: 7

1. Compounds of the formula:

in which X stands for a member of the group consisting of O and S; y stands for a member of the group consisting of hydrogen and halogen and -SO3M; and R stands for an anthraquinonyl radical of the group consisting of the unsubstituted anthraquinonyl radical and the anthraquinonyl radical which carries a substituent of the group consisting of halogen, methyl, methoxy and benzoylamino groups, there being present in the molecule at least one SO3M group attached in the beta position to one of the anthraquinone nuclei but in which neither anthraquinone nucleus carries more than one SO3M group, and in which M in each case stands for an element of the group consisting of hydrogen and an alkali metal.

2. The compound of the formula:

3. The ccimpound oi the ffifmk'lfa f 4. The compound of the formula:

References Citedi'n the file of figi ten t' UNITED STATES. P TENTS W OTHER REFERENC S T; GeorgievicsetaL, Dye Chemibtlr y "jigzG -ppefi and 

1. COMPOUNDS OF THE FORMULA 